Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
  • C08G18/7887—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having two nitrogen atoms in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3206—Polyhydroxy compounds aliphatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
  • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
  • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
  • D21H17/57—Polyureas; Polyurethanes
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/18—Reinforcing agents
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/18—Reinforcing agents
  • D21H21/20—Wet strength agents

Definitions

• the present invention relates to water-dispersible polyisocyanates, their preparation and their use for the production of re-unlockable cellulose-containing materials.
• WO 96/20309 already discloses re-unlockable cellulose-containing materials which can be produced using polyisocyanates containing ester groups. - 2 -
• the increased requirements of the paper auxiliary market do not only include a very good wet strength combined with a good re-opening of the wet-strength paper, but also a good water absorption, i.e. good absorbency of the paper, which is important for many applications.
• the paper auxiliaries known from the prior art are still in need of improvement.
• the present invention relates to water-dispersible polyisocyanates which can be obtained by reacting:
• R j stands for an alkylene radical with two to ten carbon atoms or for a radical -R- [0-R] p -, where R stands for an alkylene radical with two to ten carbon atoms and p stands for an integer from 0 to 12,
• R 2 and R 3 independently of one another represent C j - to C
• n an integer from 1 to 45, preferably from 1 to 30,
• q represents a number greater than or equal to 2
• Hydrocarbon radicals each optionally contain one or more, preferably 1 to 4, heteroatoms from the O, N, S series,
• R 5 is -CHX-CHY-, where X and Y are methyl, ethyl or hydrogen, with the proviso that if one of the substituents X and Y is methyl or ethyl, the other is always hydrogen,
• n represents an integer between 3 and 50, preferably between 3 and 25,
• R 5 has the meaning given above for formula (III),
• R 6 and R 7 independently of one another represent C2-C7-alkyl
• R 6 and R 7 together with the N atom to which they are attached represent a 5- or 6-membered heterocyclic ring, preferably morpholine,
• R 8 represents C r C 7 alkyl
• o represents an integer from 2 to 60, preferably from 2 to 30, and X "stands for an anion, in particular for halide, tosyl, trifluoromethyl sulfate, methyl sulfate, sulfate.
• the present invention furthermore relates to a process for the preparation of water-dispersible polyisocyanates by reacting
• auxiliaries and additives such as Catalysts or stabilizers known per se for water-dispersible polyisocyanate preparations and viscosity-modifying additives such as non-isocyanate-reactive solvents are also used in polyurethane chemistry.
• these “diluents” are propylene glycol diacetate and methoxypropylacetate.
• the bishydroxyl-functional compounds of structure (I) are obtainable from the dialkyl ketals of ketones or dialkylacetals from aldehydes. Among all dialkyl ketals or acetals, these are preferred, which are based on aliphatic ketones - 6 -
• aldehydes are based, for example, like acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl tertiary butyl ketone, dipropyl ketone, dinonyl ketone, 2-undecanone and from these by reaction with monoalcohols such as methanol, ethanol, propanol, iroprop. Butanols, pentanols or higher molecular weight monoalcohols such as fatty alcohols, such as stearyl alcohol, are available.
• aliphatic aldehydes examples include: formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, pivalinaldehyde, enanthaldehyde, 2-ethylhexanal and higher aldehydes.
• the dialkylacetals can be obtained from the aldehydes by reaction with the above-mentioned monoalcohols.
• dialkyl ketals or acetals are by means of acidic catalysts such as p-toluenesulfonic acid, trifluoromethylsulfonic acid, acidic ion exchangers or alkaline catalysts such as sodium methylate,
• Sodium ethylate, sodium isopropylate with known diols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, oligomeric polyethylene or polypropylene glycols up to a molecular weight of up to 350, 1,3-propanediol, 1,4-butanediol, pentanediol-1 , 5, neopentyl glycol, 1,6-hexanediol, 3-methylpentanediol-1, 5, 2,5-hexanediol.
• the bishydroxyl-functional compounds of structure (I) are prepared by transketalization or transacetalization of the dialkyl ketals or acetals, aliphatic ketones or aldehydes with diols, while at the same time distilling off the alcohol formed. If suitable solvents are used, the alcohol can also be distilled off as an azeotrope with the solvent. Suitable catalysts for this reaction are acidic and basic substances such as p-toluenesulfonic acid or sodium methylate, but also with water. - 7 -
• Ion exchangers loaded with material ions. This reaction produces oligomeric structures with terminal hydroxyl functions.
• a variant of the process consists in using an excess of the diols and, after the transketalization or acetalization has taken place, the excess diol is removed again under gentle conditions, if appropriate by thin-layer distillation. The manufactured in this way
• Oligoketals or acetals can be used directly in the reaction with isocyanates.
• Preferred bishydroxyl-functional compounds (I) are oligomeric reaction products of acetone dialkyl ketals with oligomeric polyethylene glycols.
• polyisocyanates of structure (II) aliphatic, cycloaliphatic, araliphatic or aromatic isocyanates of the NCO functionality from 1.8 to 4.2.
• Polyisocyanates are preferably used which have isocyanurate and / or allophanate and / or biuret and / or oxadiazine structures and are obtainable in a manner known per se by appropriate “modification” from aliphatic, cycloaliphatic, araliphatic or aromatic diisocyanates
• Such polyisocyanates (II) are described, for example, in DE-A 28 32 253, pages 10 to 11.
• Polyether alcohols of structure (III) are monohydric polyalkylene oxide polyether alcohols having a statistical average of 2 to 70, preferably 2 to 60, polyalkylene oxide units per molecule, as can be obtained in a manner known per se by alkoxylation of suitable starter molecules.
• Any monohydric alcohols in the molecular weight range from 32 to 150 g / mol can be used as starter molecules to produce these polyalkylene oxide polyether alcohols.
• Monofunctional aliphatic alcohols having 1 to 4 carbon atoms are preferably used as starter molecules.
• the use of methanol or ethylene glycol monomethyl ether is particularly preferred.
• Alkylene oxides suitable for the alkoxylation reaction are, in particular, ethylene oxide, propylene oxide and butylene oxide, which can be used in the alkoxylation reaction in any order or in a mixture.
• Preferred polyether alcohols (III) are methoxypolyethylene glycols in the molecular weight range 150 to 1000.
• polyalkylene oxide polyester ethers which are not described by the structure (III) and which are obtained by reacting aliphatic dicarboxylic acids having 2 to 8 carbon atoms or their esters or acid chlorides with polyethers from the group consisting of the polyethylene glycols, polypropylene glycols or their mixed polyether forms or simple mixtures are accessible from both and have an average molecular weight below 10,000 g / mol, preferably below 3000 g / mol, and are terminated by hydroxyl functions.
• Quaternized aminopolyalkylene oxide polyether alcohols of structure (IV) are known per se from EP-A 109 354 and EP-A 335 115.
• the compounds (IV) are preferably prepared so that at least one tert.
• Amino alcohols with a molecular weight of up to 150 g / mol can be used as starter molecules.
• Preferred starter molecules are at least one tert. ⁇ ⁇ mino-functional aliphatic alcohols with up to 15 carbon atoms turns.
• Particularly preferred starter molecules are monofunctional tert. Amino alcohols with up to 10 carbon atoms are used.
• the quaternization of the tert. Amino function can take place both before and after the alkoxylation.
• alkoxylation is carried out using known prior art processes with known alkylating agents.
• alkylating agents include: dialkyl sulfates, alkyl chlorides, alkyl bromides, alkyl iodides, toluenesulfonic acid alkyl esters, alkyl phosphonic acid esters and trifluoromethylsulfonic acid alkyl esters.
• Alkylating agents with an alkyl radical of one to seven carbon atoms are preferred.
• Methyl compounds, in particular methyl chloride, dimethyl sulfate, are particularly preferred.
• Alkylene oxides suitable for the alkoxylation reaction are, in particular, ethylene oxide, propylene oxide and / or butylene oxide, which can be used in the alkoxylation reaction in any order or in a mixture.
• Amino groups or their quaternized alcohol-containing polyalkylene oxide polyether alcohols are preferably pure polyethylene oxide polyethers or mixed polyalkylene oxide polyethers which have at least one polyether sequence which has at least 2, generally 2 to 70, preferably 2 to 60, particularly preferably 2 to 50, Has ethylene oxide units, and their alkylene oxide units consist of at least 60 mol%, preferably at least 70 mol%, of ethylene oxide units.
• Preferred such polyethylene oxide polyether alcohols are monofunctional, on an aliphatic, tert. Amino functions or their alkylated form, up to 10 carbon atoms alcohol started polyalkylene oxide polyether, which contain on average 2 to 60 ethylene oxide units.
• polyethers can also contain ester groups; but then they are less preferred. - 10 -
• polyisocyanate preparations according to the invention can be used either separately or in a mixture or in combination with external ionic or nonionic emulsifiers.
• emulsifiers are described, for example, in Houben-Weyl, "Methods of Organic Chemistry", Thieme-Verlag, Stuttgart (1961), Vol. XIV / 1,
• the output components are in any order with the exclusion of
• Alkyl ether acetate glycol diether, toluene, carboxylic acid ester, acetone, methyl ethyl ketone, tetrahydrofuran, dimethylformamide, methoxypropyl acetate or mixtures thereof.
• the reaction can be accelerated by known catalysts such as dibutyltin dilaurate, tin (II) octoate or 1,4-diazabicyclo [2,2,2] octane in amounts of 10 to 1,000 ppm, based on the reaction components.
• the reaction is carried out at temperatures up to 130 ° C., preferably at 10 ° C. to 100 ° C., particularly preferably at 20 ° C. to 80 ° C.
• the reaction can be followed by titration of the NCO content or by evaluating the NCO band of the IR spectrum at 2260 to 2275 cm ⁇ l and is complete when the isocyanate content does not exceed 0.1% by weight.
• Components a) to d) are preferably used in the following amounts:
• Component a 10 to 50 parts by weight
• Component b) 50 to 90 parts by weight
• Component c) 12 to 45 parts by weight
• Component d) 0 to 25 parts by weight of reaction product from a) and b): 50 to 80 parts by weight
• the polyisocyanates according to the invention are water-dispersible. This means that they are polyisocyanates which, in a concentration of up to 70% by weight, preferably 0.05 to 70% by weight, in particular 0.05 to 10% by weight, in water, have finely divided dispersions with particle sizes of below 500 nm, in particular from 80 to 500, preferably 100 to 350 nm. These aqueous dispersions of the polyisocyanates according to the invention are also the subject of the present invention.
• the aqueous dispersions according to the invention can be other conventional ones
• Auxiliaries and additives e.g. Contain solvents, stabilizers.
• the polyisocyanates according to the invention are technically easy to handle and stable in storage for months with the exclusion of moisture.
• the mixing units customary in technology (stirrers, mixers with a rotor-stator principle and e.g. high-pressure emulsifying machines) are suitable for dispersion.
• the preferred polyisocyanates according to the invention are self-emulsifying, ie they can be easily emulsified after addition to the water phase even without the action of high shear forces.
• a static mixer is usually sufficient.
• the dispersions obtained according to the invention have a certain processing time, which is from - 12 -
• the structure of the polyisocyanates to be used according to the invention in particular depends on their content of basic N atoms.
• the processing time of such an aqueous emulsion is usually up to 24 hours.
• the processing time is defined as the time in which the optimum dry and wet strength effect is achieved.
• the water-dispersible polyisocyanate in solution in a solvent which is inert to isocyanate groups.
• Suitable solvents are, for example, those mentioned above.
• the proportion of solvents in the solution of the polyisocyanate should be at most 80% by weight, preferably at most 50% by weight.
• the use of solvent-free, water-dispersible polyisocyanates according to the invention is particularly preferred.
• Another object of the present invention is the use of the aqueous polyisocyanate dispersions according to the invention for the refinement of cellulose-containing materials.
• Suitable cellulose-containing materials are, in particular, paper, cardboard or cardboard, each of which may also contain .particles. Of wood fibers (wood pulp).
• Refinement is understood to mean the dry and wet strength finishing of the materials mentioned.
• the aqueous polyisocyanate dispersions can be used in bulk for dry and wet-strength finishing; they are then preferably added directly to the cellulose-containing dispersion of the fiber raw materials.
• the polyisocyanate according to the invention is dispersed in water at 20 to 80 ° C. and the dispersion obtained is added to a suspension of the fiber raw material or it is dispersed directly in the suspension of the fiber materials. This suspension is formed by dewatering - 13 -
• a finished base paper is treated with an aqueous polyisocyanate dispersion according to the invention and then dried. Use in the size press is possible.
• the polyisocyanate dispersed in water is transferred to the finished paper web.
• Testing will generally form paper sheets with a basis weight of 50 to 100 g / m 2 in the laboratory.
• the products in the pH range from 4 to 10, preferably from 5.5 to 9, can be metered in bulk to the solid.
• aqueous polyisocyanate dispersion according to the invention depend on the desired effect. In general, amounts of 0.001 to 50% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.1 to 2.0% by weight, of active compound, based on dry fiber raw material, are sufficient.
• the dosage of active substance, based on fiber raw material corresponds to that of known ones
• aqueous polyisocyanate dispersions to be used according to the invention produce ready-to-use papers with good wet strength from the machine. By storing the finished paper and / or post-condensation, an increase in the wet strength effect can be achieved.
• the dry strength is also better than conventional - 14 -
• the papers obtained have an improved absorbency.
• the inventive use of the aqueous polyisocyanate dispersions for finishing is carried out at the usual working temperatures in the paper industry.
• the processing time depends on the temperature.
• the processing time is relatively long in the temperature range of 20 to 25 ° C.
• the wet strength effect still reaches approximately 70% of the value when the dispersion is used immediately.
• processing within 6 hours is recommended.
• the maximum wet strength effect however, surprisingly hardly depends on the contact time with the cellulose. Papers that were formed immediately and after a contact time of 2 hours after the addition to the paper pulp each show the same wet strength.
• the strength of the paper can be adjusted in the desired manner by a suitable choice of the starting components.
• aqueous polyisocyanate dispersions according to the invention can be used in combination with other cationic auxiliaries, such as retention aids, fixing aids, drying aids and wet strength agents.
• cationic auxiliaries such as retention aids, fixing aids, drying aids and wet strength agents.
• retention agents of the cationic polycondensate and polymer type e.g. the polyamides, the polyethyleneimines, the polyamidamines and the polyacrylamides and the dual systems consisting of cationic or cationic and anionic and, if appropriate, particulate components such as silica sols, etc.
• the fixation of fillers can be further strengthened.
• Preferred retention agents for the purposes of the invention are cationic polycondensates made from polyamines, preferably with dichloroethane.
• the desired wet strength effect can also be achieved without the addition of special fixing aids.
• the strength of the paper can in particular - 15 -
• polysaccharides such as hydroxyethyl cellulose, carboxymethyl cellulose, starch, galactomarmans or their cationic derivatives.
• Dispersions optionally together with the cationic auxiliaries mentioned above, i.e. used simultaneously or in succession.
• auxiliaries since many of the auxiliaries contain organically bound halogen, a combination with auxiliaries free of AOX and / or low in AOX is particularly preferred since chlorine-free paper production is the primary objective.
• All cellulose-containing materials such as paper, cardboard or cardboard produced using the aqueous polyisocyanate dispersions according to the invention can be re-opened.
• reaction times since these depend to a large extent on the degree of wet consolidation and, for example, on the weight per unit area of the cellulosic materials to be re-opened.
• water-dispersible polyisocyanates described last, be it in substance or in aqueous suspension, to produce chemically or biodegradable coating agents, adhesives, binders or plastics.
• a monofunctional ether of structure III a methoxypolyethylene glycol with an average molecular weight of 500
• a polyether started on morpholinoethanol based on ethylene oxide with a number average molecular weight of 428 g / mol and an OH number of 131 mg KOH / g.
• This polyether is reacted with toluenesulfonic acid methyl ester in a stoichiometric ratio of 1: 1. Its OH number is then 89 mg KOH / g.
• isocyanate preparations 1 to 3 Different degrees of hydrophilization and cationization were realized; the preparations produced are referred to as isocyanate preparations 1 to 3. Their composition can be seen in the following table.
• the isocyanate preparations 1 to 3 are readily dispersible in water.
• An isocyanate preparation consisting of:
• Birch sulfate pulp is ground to a freeness of 38 ° SR at a consistency of 2.5%. Then in each case 100 g of the pulp suspension obtained are diluted in beakers with water to a volume of 1000 ml.
• the results for the wet breaking load and for the wet absorption are better the larger the numerical value determined, while the values of the wet breaking load after NaOH treatment are the better, the smaller the numerical value found is the residual wet breaking load.
• the values determined for the residual wet breaking load in this way are a measure of the re-opening of the wet-strength paper.
• the measured values found show that the isocyanate preparations according to the invention improve the achievable wet break loads, the residual wet break loads and the wet absorption.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)
• Polymerisation Methods In General (AREA)

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• 1998
  • 1998-03-06 DE DE19809669A patent/DE19809669A1/de not_active Withdrawn
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